Fe<sub>3</sub>O<sub>4</sub>-BiOBr/Graphene磁性气凝胶的构筑与Cr(VI)污水净化

铁伟伟; 邱帅彪; 王红霞; 袁双义; 董旭; 何伟伟

doi:10.13801/j.cnki.fhclxb.20230911.001

Fe₃O₄-BiOBr/Graphene磁性气凝胶的构筑与Cr(VI)污水净化

doi: 10.13801/j.cnki.fhclxb.20230911.001

许昌学院　化工与材料学院(表面微纳米材料研究所)，河南省微纳米能量储存与转换材料实验室，许昌 461000

基金项目: 河南省国家级大学生创新创业训练项目 (202110480014)；河南省高等学校青年骨干教师培养计划(2021GGJS145)；河南省高等学校重点科研项目(22A430036)

详细信息

通讯作者:
铁伟伟，博士，副教授，研究方向为纳米光电材料　E-mail: tieww929@163.com

中图分类号: O614.24+；TB333
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出版历程
- 收稿日期: 2023-06-13
- 修回日期: 2023-08-18
- 录用日期: 2023-08-29
- 网络出版日期: 2023-09-12
- 刊出日期: 2024-04-01

Construction of magnetic Fe₃O₄-BiOBr/Graphene aerogel and Cr(VI) wastewater purification

Key Laboratory of Micro-Nano Materials for Energy Storage and Conversion of Henan Province, Institute of Surface Micro and Nano Materials, College of Chemical and Materials Engineering, Xuchang University,Xuchang 461000, China

Funds: National Innovation and Entrepreneurship Training Program for College Students of Henan Province (202110480014); Youth Backbone Teacher Funding Project in Universities of Henan Province (2021GGJS145); Key Scientific Research Project in Universities of Henan Province (22A430036)

摘要

摘要: 为改善单一半导体粉体材料的光生电子-空穴分离和回收能力，基于功能协同效应，采用共沉淀法，将Fe³⁺/Fe²⁺盐在一定浓度的氨水作用下制备出纳米Fe₃O₄，并分散于含有溴化十六烷基三甲铵(CTAB)的正辛烷中，提供Br^–的同时，在室温下与水溶液中的硝酸铋和柠檬酸相互作用，利用非互溶体系，制备出Fe₃O₄-BiOBr；最后，将Fe₃O₄-BiOBr分散于含有赖氨酸的氧化石墨烯水溶液中，通过一步水热法合成Fe₃O₄-BiOBr协同修饰的磁性石墨烯气凝胶(Fe₃O₄-BiOBr/Graphene)。样品的晶体结构、形貌特征和催化活性通过XRD、Raman、XPS、SEM、TEM、UV-Vis光谱等综合测试技术进行了表征分析。Fe₃O₄-BiOBr/Graphene复合材料中的Fe₃O₄呈类球状，尺寸约10~25 nm，均匀镶嵌于BiOBr片层中间，并与石墨烯之间相互作用，整体呈现球-片-空洞构造。Fe₃O₄-BiOBr/Graphene复合材料显示出良好的可见光吸收性和Cr(VI)还原活性，30 min内可去除Cr(VI)至100%，高于单一组分的磁性Fe₃O₄，这可能与Fe₃O₄-BiOBr异质结构、石墨烯导电材料的引入及Fe₃O₄-BiOBr/Graphene三者之间良好的界面相互作用，有效地促进了光生电子与空穴的分离效率有关。
- 溴氧化铋 /
- 四氧化三铁 /
- 石墨烯气凝胶 /
- 六价铬 /
- 磁性回收 /
- 光催化还原
Abstract: In order to improve the photogenerated electron-hole separation and recycling ability of single semiconductor powder material, based on the functionally synergistic effect, magnetic graphene aerogel (Fe₃O₄-BiOBr/graphene) modified by Fe₃O₄-BiOBr had been facilely prepared by one-step hydrothermal process by dispersing Fe₃O₄-BiOBr composite in aqueous solution of graphene oxide containing lysine. The Fe₃O₄-BiOBr composite was synthesized in non-miscible solvent system under room-temperature, in which nano Fe₃O₄, firstly prepared by co-precipitation method using Fe³⁺/Fe²⁺ salt under the action of ammonia water with a certain concentration, was dispersed in n-octane containing hexadecyl trimethyl ammonium bromide (CTAB) for providing Br^–, interacting with an aqueous solution containing bismuth nitrate and citric acid adding drop by drop. The crystal structure, morphology and catalytic activity of the samples were characterized by XRD, Raman, XPS, SEM, TEM, and UV-Vis spectra. Fe₃O₄-BiOBr/graphene composites, in which spherical Fe₃O₄ with a size of 10-25 nm are evenly embedded in layered BiOBr flakes, and they interact with graphene, overall, have showed a sphere-sheet-cavity structure. Fe₃O₄-BiOBr/graphene composites have favorable visible light absorption efficiency and Cr(VI) photocatalytic activity. The photocatalytic activity of Cr(VI) could achieve about 100% within 30 min, which is higher than that of single magnetic Fe₃O₄. This phenomenon maybe origin from the introduction of Fe₃O₄-BiOBr heterostructure and conductive graphene as well as their good interfacial interaction within them, effectively promoting the separation efficiency of photogenerated electrons and holes between Fe₃O₄-BiOBr/graphene composite.
- BiOBr /
- Fe₃O₄ /
- graphene aerogel /
- Cr(VI) /
- magnetic recovery /
- photocatalytic reduction

HTML全文

图 1 Fe₃O₄-BiOBr/Graphene-1的宏观照片

Figure 1. Photographs of Fe₃O₄-BiOBr/Graphene-1

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图 2 Fe₃O₄ (a)、Fe₃O₄-BiOBr (b)和Fe₃O₄-BiOBr/Graphene-1 ((c), (d))的SEM图像

Figure 2. SEM images of Fe₃O₄ (a), Fe₃O₄-BiOBr (b) and Fe₃O₄-BiOBr/Graphene-1 ((c), (d))

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图 3 Fe₃O₄-BiOBr/Graphene-1的TEM图像

Figure 3. TEM image of Fe₃O₄-BiOBr/Graphene-1

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图 4 Fe₃O₄、BiOBr、Fe₃O₄-BiOBr和Fe₃O₄-BiOBr/Graphene-1的XRD图谱

Figure 4. XRD patterns of Fe₃O₄, BiOBr, Fe₃O₄-BiOBr and Fe₃O₄-BiOBr/Graphene-1

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图 5 氧化石墨烯(GO)和Fe₃O₄-BiOBr/Graphene-1的拉曼图谱

Figure 5. Raman spectra of graphene oxide (GO) and Fe₃O₄-BiOBr/Graphene-1

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图 6 Fe₃O₄、Fe₃O₄-BiOBr和Fe₃O₄-BiOBr/Graphene-1的XPS图谱(a)及Fe2p (b)和Bi4f (c)的XPS高分辨图谱

Figure 6. XPS spectra (a) and Fe2p (b), Bi4f (c) XPS high-resolution spectra of Fe₃O₄, Fe₃O₄-BiOBr and Fe₃O₄-BiOBr/Graphene-1

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图 7 Fe₃O₄、BiOBr、Fe₃O₄-BiOBr和Fe₃O₄-BiOBr/Graphene-1的UV-Vis DRS光谱图

Figure 7. UV-Vis DRS spectra of Fe₃O₄, BiOBr, Fe₃O₄-BiOBr and Fe₃O₄-BiOBr/Graphene-1

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图 8 Fe₃O₄-BiOBr/Graphene系列样品在模拟太阳光照射下对Cr(VI)的光催化活性曲线

Figure 8. Photocatalytic activity curves of Cr(VI) in the presence of series of Fe₃O₄-BiOBr/Graphene samples under sunlight irradiation

C_t—Concentration of Cr(VI) at time t; C₀—Initial concentration of Cr(VI)

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图 9 Fe₃O₄-BiOBr/Graphene-1的电子顺磁共振(ESR)图谱

Figure 9. Electron spin resonance (ESR) spectra of Fe₃O₄-BiOBr/Graphene-1

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图 10 Fe₃O₄和Fe₃O₄-BiOBr/Graphene-1的磁滞回线图谱

Figure 10. Hysteresis loop spectra of Fe₃O₄ and Fe₃O₄-BiOBr/Graphene-1

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图 11 Fe₃O₄、BiOBr、Fe₃O₄-BiOBr和Fe₃O₄-BiOBr/Graphene-1的瞬态光电流图谱

Figure 11. Photocurrent spectra of Fe₃O₄, BiOBr, Fe₃O₄-BiOBr and Fe₃O₄-BiOBr/Graphene-1

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图 12 模拟太阳光下Fe₃O₄-BiOBr/Graphene-1复合材料对污染物Cr(VI)的光催化还原示意图

Figure 12. Photocatalytic reduction mechanism of Fe₃O₄-BiOBr/Graphene-1 composite onto Cr(VI) under sunlight irradiation

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表 1 系列Fe₃O₄-BiOBr/Graphene气凝胶

Table 1. Series of Fe₃O₄-BiOBr/Graphene aerogel

Sample	Graphene oxide/(g·mL⁻¹)	Fe₃O₄-BiOBr/g
Fe₃O₄-BiOBr/Graphene-1	4.2	0.40
Fe₃O₄-BiOBr/Graphene-2	5.0	0.35
Fe₃O₄-BiOBr/Graphene-3	5.0	0.40
Fe₃O₄-BiOBr/Graphene-4	3.5	0.40

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表 2 Fe₃O₄-BiOBr/Graphene-1气凝胶的物理性能

Table 2. Physical properties of Fe₃O₄-BiOBr/Graphene-1 aerogel

Sample	BET surface area/(m²·g⁻¹)	Pore size/ nm (4 V/A by BET)	Pore volume / (cm³·g⁻¹)	Porosity/ %
Fe₃O₄-BiOBr/ Graphene-1	47.8902	17.14143	0.205227	85.5914
Note: BET—Brunauer-Emmett-Teller.

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